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Chiral Memory in Silylium Ions
Author(s) -
Ducos P.,
Liautard V.,
Robert F.,
Landais Y.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501987
Subject(s) - chirality (physics) , lewis acids and bases , silicon , epimer , diastereomer , lone pair , ion , solvent , chelation , chemistry , base (topology) , catalysis , crystallography , materials science , stereochemistry , inorganic chemistry , organic chemistry , molecule , physics , chiral symmetry , mathematics , mathematical analysis , quantum mechanics , nambu–jona lasinio model , quark
The configurational stability of the chiral silicon center in Lewis base‐stabilized silyliums has been studied. Complete retention of configuration at silicon is observed at low temperature in silylium ions stabilized by lone‐pair interactions. In contrast, loss of chiral memory is observed with systems involving π‐interactions. Epimerization of the silicon center was observed by simply allowing equilibration of the diastereomeric silyliums at RT or by adding a catalytic amount of a chelating solvent. Conditions for the transfer of axial chirality to Si‐centered chirality were shown to rely on the strength of the Lewis base‐silylium ion interaction.